Rate Constants for the Gas-Phase Reactions of OH and O3 with β-Ocimene, β-Myrcene, and α- and β-Farnesene as a Function of Temperature
Rate Constants for the Gas-Phase Reactions of OH and O3 with β-Ocimene, β-Myrcene, and α- and β-Farnesene as a Function of Temperature
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DOI：
10.1021/jp111173s
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发表时间：
2011-02-03
影响因子：
2.9
通讯作者：
Hites, Ronald A.
中科院分区：
文献类型：
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作者：
Kim, Daekyun;Stevens, Philip S.;Hites, Ronald A.
用相对速率法测定了在313 ~ 423 K （OH）和298 ~ 318 K （O-3）温度范围内，在1atm总压下羟基自由基和臭氧与生物烃-辛烯、-月桂烯、-和-法尼烯气相反应的速率常数。OH自由基由H2O2光解生成，O-2电解生成O-3。氦气被用作稀释气体。通过在线质谱法检测反应物，具有高时间分辨率，可以收集大量数据并用于测定Arrhenius参数。这些反应的阿伦尼乌斯表达式如下(单位为cm(3)个分子（-1）s(-1))：对于-ocimene + OH， k = (4.35（-0.66)(+0.78)） × 10(-11) exp[-(579 +/- 59)/T]；beta-ocimene + O-3, k = (3.15) (-0.95) (+ 1.36) x 10 (-15) exp (- (626 + / - 110) / T);beta-myrcene + O-3, k = (2.21) (-0.66) (+ 0.94) x 10 (-15) exp (- (520 + / - 109) / T);对于a-法尼烯+ OH， k(OH) = (2.19 +/- 0.11) × 10(-10)，为323 ~ 413 k；alpha-farnesene + O-3, k = (3.52) (-2.54) (+ 9.09) x 10 (-12) exp (- (2589 + / - 393) / T);对于-法尼烯+ OH， k(OH) = (2.88 +/- 0.15) × 10(-10)，为323 ~ 423 k；对于-法尼烯+ O-3， k = (1.811) × 10(-12) exp[-(2347 +/- 329)/T]。这里的阿伦尼乌斯参数是第一个被报道的。-和-法尼烯与OH的反应没有明显的温度依赖性。还给出了与OH和O-3反应的大气停留时间。
The rate constants for the gas-phase reactions of hydroxyl radicals and ozone with the biogenic hydrocarbons beta-ocimene, beta-myrcene, and alpha- and beta-farnesene were measured using the relative rate technique over the temperature ranges 313-423 (for OH) and 298-318 K (for O-3) at about 1 atm total pressure. The OH radicals were generated by photolysis of H2O2, and O-3 was produced from the electrolysis of O-2. Helium was used as the diluent gas. The reactants were detected by online mass spectrometry, which resulted in high time resolution, allowing large amounts of data to be collected and used in the determination of the Arrhenius parameters. The following Arrhenius expressions have been determined for these reactions (in units of cm(3) molecules(-1) s(-1)): for beta-ocimene + OH, k = (4.35(-0.66)(+0.78)) x 10(-11) exp[-(579 +/- 59)/T]; for beta-ocimene + O-3, k = (3.15(-0.95)(+1.36)) x 10(-15) exp[-(626 +/- 110)/T]; for beta-myrcene + O-3, k = (2.21(-0.66)(+0.94)) x 10(-15) exp[-(520 +/- 109)/T]; for a-farnesene + OH, k(OH) = (2.19 +/- 0.11) x 10(-10) for 323-413 K; for alpha-farnesene + O-3, k = (3.52(-2.54)(+9.09)) x 10(-12) exp[-(2589 +/- 393)/T]; for beta-farnesene + OH, k(OH) = (2.88 +/- 0.15) x 10(-10) for 323-423 K; for beta-farnesene + O-3, k = (1.811) x 10(-12) exp[-(2347 +/- 329)/T]. The Arrhenius parameters here are the first to be reported. The reactions of alpha- and beta-farnesene with OH showed no significant temperature dependence. Atmospheric residence times due to reactions with OH and O-3 were also presented.